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| United States Patent |
5,247,035
|
|
Besecke
, et al.
|
September 21, 1993
|
Soluble polymers
Abstract
At least 95% tetrahydrofuran soluble polymers are obtainable by
copolymerization of a monomer mixture of
A) from 1 to 99% by weight of at least one at least 98% pure monomer of the
general formula I
CH.sub.2 .dbd.C(E)CH.sub.2 --O--CH.sub.2 C(E').dbd.CH.sub.2 I
where E and E' have been selected from the group consisting of
--COOR.sup.1, --COR.sup.1, --CONR.sup.2 R.sup.3 and --CN and R.sup.1,
R.sup.2 and R.sup.3 are each defined as follows:
R.sup.1 =H, alkyl, cycloalkyl, cycloalkylalkyl, wherein the cycloalkyl
rings may be alkyl- or alkoxy-monosubstituted, -disubstituted or
-trisubstituted, hydroxyalkyl, aminoalkyl, alkylaminoalkyl,
dialkylaminoalkyl, aryl, arylalkyl, wherein the aryl groups may carry up
to three of the following groups: halogen, alkyl, alkoxy, carboxyl,
alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,
nitrilo, nitro, amino, alkylamino, dialkylamino;
R.sup.2, R.sup.3 =H, alkyl, cycloalkyl, cycloalkylalkyl, wherein the
cycloalkyl rings may be alkyl- or alkoxy-monosubstituted, -disubstituted
or -tri-substituted, aryl, arylalkyl, wherein the aryl groups may carry up
to three of the following groups: halogen, alkyl, alkoxy, carboxyl,
alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl,
nitrilo, nitro, amino, alkylamino, dialkylamino; and
B) from 99 to 1% by weight of at least one further radical polymerizable
monomer.
| Inventors:
|
Besecke; Siegmund (Hameln, DE);
Deckers; Andreas (Ludwigshafen, DE);
Lauke; Harald (Mannheim, DE)
|
| Assignee:
|
BASF Aktiengesellschaft (Ludwigshafen, DE)
|
| Appl. No.:
|
005781 |
| Filed:
|
January 19, 1993 |
Foreign Application Priority Data
| Current U.S. Class: |
526/244; 526/245; 526/247; 526/248; 526/292.3; 526/298; 526/304; 526/309; 526/311; 526/312; 526/316; 526/318.1; 526/320 |
| Intern'l Class: |
C08F 222/30; C08F 222/20 |
| Field of Search: |
526/320,309,316,304,298,244
|
References Cited
U.S. Patent Documents
| 4889948 | Dec., 1989 | Mathias et al. | 560/181.
|
Other References
L. J. Mathias et al. (1988) Polym Preprints 29CV, 329-330.
Journal of Polymer Science C. Letters Edition 25(1987) 451 Mathias, L. J. &
Kusefoglu, Srl.
|
Primary Examiner: Schofer; Joseph L.
Assistant Examiner: Nagumo; Mark
Attorney, Agent or Firm: Keil & Weinkauf
Claims
We claim:
1. At least 95% tetrahydrofuran soluble polymers obtained by
copolymerization of a monomer mixture of
A) from 1 to 99% by weight of at least one at least 98% pure monomer of the
general formula I
CH.sub.2 .dbd.C(E)CH.sub.2 --O--CH.sub.2 C(E').dbd.CH.sub.2 I
where E and E' have been selected from the group consisting of
--COOR.sup.1, --COR.sup.1, --CONR.sup.2 R.sup.3 and --CN and R.sup.1,
R.sup.2 and R.sup.3 are each defined as follows:
R.sup.1 =H, C.sub.1 -C.sub.18 -alkyl, C.sub.3 -C.sub.8 -cycloalkyl, C.sub.3
-C.sub.8 -cycloalkyl-C.sub.1 -C.sub.5 -alkyl, wherein the cycloalkyl rings
may be C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4 -alkoxy-
monosubstituted, -disubstituted or -trisubstituted, hydroxy-C.sub.1
-C.sub.5 -alkyl, amino-C.sub.1 -C.sub.5 -alkyl,N-C.sub.1 -C.sub.4
-alkylamino-C.sub.1 -C.sub.5 -alkyl, N,N-di(C.sub.1 -C.sub.4
-alkyl)amino-C.sub.1 -C.sub.5 -alkyl, C.sub.6 -C.sub.18 -aryl, C.sub.6
-C.sub.18 -aryl-C.sub.1 -C.sub.4 -alkyl, wherein the aryl groups may carry
up to three of the following groups: halogen, C.sub.1 -C.sub.22 -alkyl,
C.sub.1 -C.sub.4 -alkoxy, carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl,
aminocarbonyl, C.sub.1 -C.sub.4 -alkyl-aminocarbonyl, di(C.sub.1 -C.sub.4
-alkyl)aminocarbonyl, nitrilo, nitro, amino, C.sub.1 -C.sub.4 -alkylamino,
di(C.sub.1 -C.sub.4 -alkyl)amino;
R.sup.2, R.sup.3 =H, C.sub.1 -C.sub.18 -alkyl, C.sub.3 -C.sub.8
-cycloalkyl, C.sub.3 -C.sub.8 -cycloalkyl-C.sub.1 -C.sub.5 -alkyl, wherein
the cycloalkyl rings may be C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4
-alkoxy- monosubstituted, -di-substituted or -trisubstituted, C.sub.6
-C.sub.18 -aryl, C.sub.6 -C.sub.18 -aryl-C.sub.1 -C.sub.4 -alkyl, wherein
the aryl groups may carry up to three of the following groups: halogen,
C.sub.1 -C.sub.22 -alkyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl, C.sub.1
-C.sub.4 -alkoxycarbonyl, aminocarbonyl, C.sub.1 -C.sub.4
-alkylaminocarbonyl, di(C.sub.1 -C.sub.4 -alkyl)aminocarbonyl, nitrilo,
nitro, amino, C.sub.1 -C.sub.4 -alkylamino, di(C.sub.1 -C.sub.4
-alkyl)amino; and
B) from 99 to 1% by weight of at least one further radical polymerizable
monomer.
2. At least 95% tetrahydrofuran soluble polymers as claimed in claim 1,
wherein the further radical polymerizable monomer used is a mixture
comprising
from 1 to 99% by weight of C.sub.1 -C.sub.20 -alkyl methacrylate,
from 0 to 20% by weight of C.sub.1 -C.sub.20 -alkyl acrylate, and
from 0 to 20% by weight of other monomers.
3. At least 95% tetrahydrofuran soluble polymers as claimed in claim 1,
wherein the monomer mixture has had added to it
from 0 to 5% by weight of a crosslinker containing methacryloyl or acryloyl
groups, and
from 0 to 5% by weight of a demolding aid.
4. At least 95% tetrahydrofuran soluble polymers as claimed in claim 1, for
which the polymerization is carried out in the presence of a transfer
regulator.
5. A process for preparing at least 95% tetrahydrofuran soluble polymers as
claimed in claim 1, which comprises polymerizing a monomer mixture of
A) from 1 to 99% by weight of at least one at least 98% pure monomer of the
general formula I, and
B) from 99 to 1% by weight of at least one further radical polymerizable
monomer with or without a transfer regulator.
Description
The present invention relates to at least 95% tetrahydrofuran soluble
polymers obtainable by copolymerization of a monomer mixture of
A) from 1 to 99% by weight of at least one at least 98% pure monomer of the
general formula I
CH.sub.2 .dbd.C(E)CH.sub.2 --O--CH.sub.2 C(E').dbd.CH.sub.2 I
where E and E' have been selected from the group consisting of
--COOR.sup.1, --COR.sup.1, --CONR.sup.2 R.sup.3 and --CN and R.sup.1,
R.sup.2 and R.sup.3 are each defined as follows:
R.sup.1 =H, C.sub.1 -C.sub.18 -alkyl, C.sub.3 -C.sub.8 -cycloalkyl, C.sub.3
-C.sub.8 -cycloalkyl-C.sub.1 -C.sub.5 -alkyl, wherein the cycloalkyl rings
may be C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4
-alkoxy-monosubstituted, -disubstituted or -trisubstituted,
hydroxy-C.sub.1 -C.sub.5 -alkyl, amino-C.sub.1 -C.sub.5 -alkyl,N-C.sub.1
-C.sub.4 -alkylamino-C.sub.1 -C.sub.5 -alkyl, N,N-di(C.sub.1 -C.sub.4
-alkyl)amino-C.sub.1 -C.sub.5 -alkyl, C.sub.6 -C.sub.18 -aryl, C.sub.6
-C.sub.18 -aryl-C.sub.1 -C.sub.4 -alkyl, wherein the aryl groups may carry
up to three of the following groups: halogen, C.sub.1 -C.sub.22 -alkyl,
C.sub.1 -C.sub.4 -alkoxy, carboxyl, C.sub.1 -C.sub.4 -alkoxycarbonyl,
aminocarbonyl, C.sub.1 -C.sub.4 -alkylaminocarbonyl, di(C.sub.1 -C.sub.4
-alkyl)aminocarbonyl, nitrilo, nitro, amino, C.sub.1 -C.sub.4 -alkylamino,
di(C.sub.1 -C.sub.4 -alkyl)amino;
R.sup.2, R.sup.3 =H, C.sub.1 -C.sub.18 -alkyl, C.sub.3 -C.sub.8
-cycloalkyl, C.sub.3 -C.sub.8 -cycloalkyl-C.sub.1 -C.sub.5 -alkyl, wherein
the cycloalkyl rings may be C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4
-alkoxy- monosubstituted, -di-substituted or -trisubstituted, C.sub.6
-C.sub.18 -aryl, C.sub.6 -C.sub.18 -aryl-C.sub.1 -C.sub.4 -alkyl, wherein
the aryl groups may carry up to three of the following groups: halogen,
C.sub.1 -C.sub.22 -alkyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl, C.sub.1
-C.sub.4 -alkoxycarbonyl, aminocarbonyl, C.sub.1 -C.sub.4
-alkylaminocarbonyl, di(C.sub.1 -C.sub.4 -alkyl)aminocarbonyl, nitrilo,
nitro, amino, C.sub.1 -C.sub.4 -alkylamino, di(C.sub.1 -C.sub.4
-alkyl)amino; and
B) from 99 to 1% by weight of at least one further radical polymerizable
monomer.
The invention further relates to a process for preparing soluble polymers,
to their use for producing moldings, and to moldings from these polymers.
J. Appl. Polym. Sci. Polym. Letters Edition 25 (1987) 451 describes a
copolymer of methyl methacrylate (MMA) and oxadimethyl methacrylate. The
disadvantage is that the highly crosslinked copolymer, prepared by bulk
polymerization of 3.5% by weight of oxadimethyl methaacrylate and and
96.5% by weight of methyl methacrylate, is infusible and insoluble, i.e.,
of no industrial utility.
It is an object of the present invention to provide soluble,
thermoplastically processible copolymers obtainable by polymerization of
oxadimethacrylates and copolymerizable monomers.
We have found that this object is achieved by the copolymers defined at the
beginning.
We have also found a process for preparing the copolymers, their use for
producing moldings, and moldings produced therefrom.
Component A) according to the invention comprises from 1 to 99% by weight
of at least one oxadimethacrylate compound I. According to the invention,
the monomer to be used has a purity of at least 98%, preferably at least
99%, particularly preferably at least 99.2%. Monomers which do not satisfy
this purity criterion generally give highly crosslinked, insoluble and
infusible products.
The substituents on the oxadimethacrylics I preferably have the following
meanings:
R.sup.1 hydrogen;
C.sub.1 -C.sub.18 -alkyl, preferably C.sub.1 -C.sub.12 -alkyl such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl,
tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl,
n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl and
stearyl, particularly preferably C.sub.1 -C.sub.4 -alkyl such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;
C.sub.3 -C.sub.8 -cycloalkyl such as cyclopropyl, cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl, 4-methylcyclohexyl, 4-methoxycyclohexyl,
2,4,6-trimethylcyclohexyl;
C.sub.3 -C.sub.8 -cycloalkyl-C.sub.1 -C.sub.5 -alkyl such as
cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl,
cyclopentylethyl, cyclohexylethyl, cyclopropylpropyl, cyclopentylpropyl,
cyclohexylpropyl, cyclopentylbutyl, cyclohexylbutyl, cyclopentylpentyl,
cyclohexylpentyl, cyclooctylpentyl;
hydroxy-C.sub.1 -C.sub.5 -alkyl such as hydroxymethyl, 2-hydroxyethyl,
2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl,
2,2-dimethyl-3-hydroxypropyl;
amino-C.sub.1 -C.sub.5 -alkyl such as aminomethyl, 2-aminoethyl,
3-aminopropyl, 4-aminobutyl, 5-aminopentyl; N-C.sub.1 -C.sub.4
-alkylamino-C.sub.1 -C.sub.5 -alkyl such as N-methylaminomethyl,
2-(N-methylamino)ethyl, 3-(N-methylamino)propyl, 4-(N-methylamino)butyl,
5-(N-methylamino)pentyl, N-ethylaminomethyl, N-n-propylaminomethyl,
N-n-butylaminomethyl;
N,N-di(C.sub.1 -C.sub.4 -alkyl)amino-C.sub.1 -C.sub.5 -alkyl such as
N,N-dimethylaminomethyl, 2-(N,N-dimethylamino)ethyl,
3-(N,N-dimethylamino)propyl, 4-(N,N-dimethylamino)butyl,
5-(N,N-dimethylamino)pentyl, N,N-diethylaminomethyl,
N,N-di(n-propyl)aminomethyl, N,N-di(isopropyl)aminomethyl,
N,N-di(n-butyl)aminomethyl, N-ethyl-N-methyl-aminomethyl,
N-methyl-N-propyl-aminomethyl;
C.sub.6 -C.sub.18 -aryl such as phenyl, naphthyl, anthracenyl,
phenantrenyl, azulenyl, biphenylenyl, triphenylenyl, preferably phenyl, it
being possible for the aryl radicals to carry up to three of the groups
mentioned under R.sup.4 ;
C.sub.6 -C.sub.18 -aryl-C.sub.1 -C.sub.4 -alkyl, preferably phenyl-C.sub.1
-C.sub.4 -alkyl such as benzyl, 2-phenylethyl, 3-phenylpropyl,
4-phenylbutyl, particularly preferably benzyl, 2-phenylethyl,
3-phenylpropyl, it being possible for the aryl groups to carry up to three
of the groups mentioned under R.sup.4 ;
R.sup.2, R.sup.3 C.sub.1 -C.sub.18 -alkyl such as mentioned for R.sup.1,
including particularly preferably C.sub.1 -C.sub.4 -alkyl such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl;
C.sub.3 -C.sub.8 -cycloalkyl such as cyclopropyl, cyclopentyl, cyclohexyl,
cycloheptyl, cyclooctyl, 4-methylcyclohexyl, 2,4,6-trimethylcyclohexyl;
C.sub.6 -C.sub.18 -aryl as mentioned for R.sup.1, preferably phenyl, which
may carry up to three of the groups mentioned under R.sup.4 ;
C.sub.6 --C.sub.18 -aryl-C.sub.1 -C.sub.4 -alkyl such as mentioned for
R.sup.1, preferably phenyl-C.sub.1 -C.sub.4 -alkyl, particularly
preferably benzyl, 2-phenylethyl, 3-phenylpropyl, wherein the phenyl group
may carry up to three of the groups mentioned under R.sup.4 ; and
R.sup.4 halogen such as fluorine, chlorine, bromine and iodine, C.sub.1
-C.sub.22 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,
tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,
n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl,
n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl and
n-docosyl, preferably C.sub.1 -C.sub.12 -alkyl such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl,
isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl,
n-nonyl, n-decyl, n-undecyl, n-dodecyl and stearyl, particularly
preferably C.sub.1 -C.sub.4 -alkyl such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; C.sub.1 -C.sub.4
-alkoxy such as methoxy, ethoxy, n-propoxy and n-butoxy, carboxyl, C.sub.1
-C.sub.4 -alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl,
n-propoxycarbonyl and n-butoxycarbonyl, aminocarbonyl, C.sub.1 -C.sub.4
-alkylaminocarbonyl such as
methylaminocarbonyl,ethylaminocarbonyl,n-propyl-aminocarbonyl and
n-butylaminocarbonyl, di(C.sub.1 -C.sub.4 -alkyl)aminocarbonyl such as
dimethylaminocarbonyl, diethylaminocarbonyl, di(n-propyl)aminocarbonyl and
di(n-butyl)aminocarbonyl, nitrilo, nitro, amino, C.sub.1 -C.sub.4
-alkylamino such as methylamino, ethylamino, n-propylamino and
n-butylamino, di(C.sub.1 -C.sub.4 -alkyl)amino such as dimethylamino,
diethylamino, di(n-propyl)-amino and di(n-butyl)amino.
Particularly preferred oxadimethacrylics I are dimethyl
2,2'-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl
2,2'-[oxybis(methylene)]bis-2-propenoate and cyclohexyl methyl
2,2'-[oxybis(methylene)]bis-2-propenoate.
Oxadimethacrylics I are obtainable if E and F.noteq. COOH not only from
acrylics of the general formula II
H.sub.2 C.dbd.C(E)H II
but also from alcohols of the general formula III
H.sub.2 C.dbd.C(E)CH.sub.2 OH III
by reaction with formaldehyde. Their preparation is described for example
in U.S. Pat. No. 4,889,948. It is more advantageous, however, especially
if particularly pure compounds are to be obtained, to employ one of the
following methods:
A) reaction of an acrylic of the general formula II
H.sub.2 C.dbd.C(E)H II
with formaldehyde or a formaldehyde donor in the presence of oxygen, at
least one tertiary amine and preferably at least one polymerization
inhibitor to form the alcohol of the general formula III
H.sub.2 C.dbd.C(E)CH.sub.2 OH III
and subsequent conversion of the alcohol III
b.sub.1) with isolation thereof or
b.sub.2) without isolation thereof
into the oxadimethacrylic I CH.sub.2 .dbd.C(E)CH.sub.2 --O--CH.sub.2
C(E).dbd.CH.sub.2 by heating in the presence of oxygen, at least one
tertiary amine and preferably at least one polymerization inhibitor, or
B) conversion of the alcohol III into the oxadimethacrylic I CH.sub.2
.dbd.C(E)CH.sub.2 --O--CH.sub.2 C(E).dbd.CH.sub.2 by heating in the
presence of oxygen, at least one tertiary amine and preferably at least
one polymerization inhibitor, or reaction of a mixture of two different
acrylics of the general formulae II and IIa
##STR1##
with formaldehyde or a formaldehyde donor in the presence of oxygen, at
least one tertiary amine and preferably at least one polymerization
inhibitor to form the alcohols of the general formulae III and IIIa
##STR2##
and subsequent further reaction with or without further isolation of the
alcohols III and IIIa with either
a) the reaction mixture containing these alcohols, or
b) the isolated alcohols
by heating in the presence of oxygen, at least one tertiary amine and
preferably at least one polymerization inhibitor to form the
oxadimethacrylic I CH.sub.2 .dbd.C(E)CH.sub.2 --O--CH.sub.2
C(E').dbd.CH.sub.2, or
D) reaction of an acrylic II with formaldehyde or a formaldehyde donor in
the presence of oxygen, at least one tertiary amine and at least one
polymerization inhibitor to form the alcohol III and subsequent further
reaction of the isolated alcohol III or of the reaction mixture containing
the unisolated alcohol III with a further, different alcohol of the
formula IIIa by heating in the presence of oxygen, at least one tertiary
amine and preferably at least one polymerization inhibitor to form the
oxadimethacrylic I CH.sub.2 .dbd.C(E)CH.sub.2 --O--CH.sub.2
C(E').dbd.CH.sub.2, or
E) reaction of a mixture of two different alcohols II and IIa by heating in
the presence of oxygen, at least one tertiary amine and at least one
polymerization inhibitor to form the oxadimethacrylic I CH.sub.2
.dbd.C(E)CH.sub.2 --O--CH.sub.2 C(E').dbd.CH.sub.2.
The acrylics II required for these reactions are either commercially
available or obtainable by methods known per se, for example by
esterification, transesterification, amidation or aminolysis (see H.
Rauch-Puntigam et al., Chemie, Physik und Technologie der Kunststoffe,
vol. 9, Springer Verlag, Berlin, 1967), from the corresponding readily
available acrylic precursors such as acrylic acid and known derivatives
thereof.
The corresponding alcohols III are either known (see EP-B-184 731) or
obtainable from the acrylics II by one of the abovementioned methods.
The formaldehyde can be used in gas form, and liquid form, for example as
an aqueous solution such as formalin or in the form of a solution in an
alcohol, or in solid form, for example as paraformaldehyde, trioxane or
tetroxocane, or as a hemiacetal.
Suitable tertiary amines are open-chain aliphatic or cyclic tertiary amines
such as trimethylamine, tri-ethylamine, tri-n-propylamine,
triisopropylamine, tri-n-butylamine, triisobutylamine, tri-n-pentylamine,
methyl-diisopropylamine, N,N-diethylisopropylamine,
N,N-dimethylethylamine, N,N-dimethylisopropylamine, tri-2-ethylhexylamine,
N-methyldiethylamine, N,N-dimethyl-n-propylamine,
N,N-dimethyl-n-butylamine, N,N-dimethylisobutylamine,
N,N-dimethyl-(2-ethylhexyl)amine, N,N-diisopropyl-(2-ethylhexyl)amine,
N,N-di-n-butyl-(2-ethyl-hexyl)amine, N-methyl-di(2-ethylhexyl)amine,
N-n-butyl-(2-ethylhexyl)amine, N-isobutyl-di(2-ethylhexyl)amine,
quinuclidine and 1,4-diazabicyclo-[2.2.2]octane (DABCO.RTM.), preferably
quinuclidine and DABCO.RTM., particularly preferably DABCO.RTM..
The polymerization inhibitors used are in general the usual ones such as
hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, phenol,
2,6-dimethylphenol, 2,6-di-tert-butylphenol, methylene blue,
diphenylamine, cupric oleate, ferric acetylacetonate, pyrocatechol,
preferably hydroquinone monomethyl ether and hydroquinone monoethyl ether.
The oxygen can be passed in pure form or in the form of a mixture with
nonreactive gases, preferably air, over or through the reaction mixture.
In the conversion of the acrylic II or of the mixed acrylics II and IIa
into the oxadimethacrylic I via the alcohol compound III, the first stage
is in general carried out with a molar ratio of acrylic II or II/IIa to
formaldehyde of from 1:1 to 8:1, preferably from 1.0:1 to 2.5:1.
In this reaction the tertiary amine is preferably used in a molar ratio of
formaldehyde to amine of from 1:1 to 200:1.
The polymerization initiator is in general used in amounts of from 10 to
1000 mg per kg of acrylic II or of acrylics mix II-IIa.
The amount of oxygen used ranges in general from 0.01 to 100, preferably
from 0.1 to 20, l/h per kg of acrylic II or mix II and IIa. If air is used
as oxygen donor, the gas rate will in general range from 0.01 to 1000,
preferably from 1 to 250, l/h per kg of acrylic II or mix II and IIa.
The reaction is in general carried out at from 10 to 100.degree. C.,
preferably at from 40.degree. to 80.degree. C., particularly preferably at
from 60.degree. to 75.degree. C. Furthermore, the reaction is in general
carried out under atmospheric pressure. However, it can also be carried
out under reduced or superatmospheric pressure. The employment of
super-atmospheric pressure is advisable in particular when the reaction is
carried out at above 80.degree. C.
Furthermore, the reaction is in general carried out without solvent.
However, the reaction can also be carried out in the presence of a
suitable solvent such as a C.sub.5 -C.sub.8 -alkane, preferably n-pentane,
n-hexane, n-heptane, n-octane, isooctane, a carboxylic ester such as ethyl
acetate or an aromatic solvent such as benzene, toluene and xylenes,
particularly preferably n-hexane, isooctane and toluene, or mixtures
thereof.
The reaction time depends chiefly on the reaction temperature, but will in
general range from 1 to 6 h.
The resulting alcohol III or the mixture of alcohols III and IIIa can be
isolated by a conventional workup method such as distillation or
chromatography.
The second stage, starting from alcohol III or the mixture of alcohols III
and IIIa, will in general be carried out with the same type and amount of
amine, polymerization inhibitor and solvent as in the first stage. The
oxygen rate will in general be within the range from 0.01 to 1000,
preferably from 0.1 to 50, l/h per kg of alcohol compound III or mixture
of alcohol compounds III and IIIa. If air is used as oxygen donor, the gas
rate will in general be within the range from 0.1 to 1000, preferably from
1 to 500, l/h per kg of alcohol compound III or mixture of alcohol
compounds III and IIIa.
The second stage conversion reaction (alcohol III into oxadimethacrylic I)
is in general carried out at from 100.degree. to 200.degree. C.,
preferably at from 100.degree. to 150.degree. C., and at a pressure which
in general will range from 70 to 300 kPa, but which preferably will be
atmospheric pressure.
The water of reaction can in general be removed from the reaction mixture
by distillation, preferably by rectification.
For this purpose it is a good idea to add an entrainer to the reaction
mixture. Suitable entrainers for this purpose are for example aliphatic,
cycloaliphatic and aromatic hydrocarbons such as n-hexane, n-heptane,
isooctane, benzene, toluene, xylene and cyclohexane, carboxylic esters
such as ethyl acetate, or the acrylics II if it has not been separated off
prior to the reaction. The entrainer will in general be selected to have a
boiling point within the range from 80.degree. to 200.degree. C.
The reaction time is dependent on the usual parameters such as temperature,
pressure and quantities of the starting materials and will in general
range from 4 to 12 h.
If the reactions starting from the acrylic II or the mixture of acrylics II
and IIa are carried out as single stages, i.e. without isolating the
alcohol III or the mixture of alcohols III and IIIa, it is advisable to
separate off excess acrylic II, or excess mixture of acrylics II and IIa,
for example by distillation, prior to the reaction to form the
oxadimethacrylic I. However, this may also be done after the reaction to
form the oxadimethacrylic I.
It is particularly preferable, if one of the methods A), C) and D) is used,
for the acrylic II or IIa, which in general will be present in excess, to
be distilled off before the product is isolated and purified by
crystallization. It is similarly advantageous for the water of reaction
formed in the course of A) to E) to be separated off, for example by
distillation, prior to the crystallization.
To purify the oxadimethacrylic I it can be precipitated from solutions
containing at least one hydrocarbon compound that is liquid at room
temperature. This hydrocarbon compound may be present in the solutions
from the start or be added later.
In general, the precipitation will be effected directly from the reaction
mixtures, which, in general, may contain not only the oxadimethacrylic but
further compounds such as starting materials, catalysts, stabilizers, etc.
This solubility-lowering hydrocarbon compound may be added right at the
start of the preparation of the solution. However, in general it will be
advantageous not to add it to the solution containing the oxadimethacrylic
until the precipitation or crystallization is to be initiated.
The hydrocarbon compounds used will in general have boiling points within
the range from 20.degree. to 200.degree. C., preferably from 35.degree. to
130.degree. C., such as aliphatic, cycloaliphatic or aromatic hydrocarbons
or mixtures thereof. Examples are n-pentane, n-hexane, n-heptane,
n-octane, n-nonane, n-decane and branched isomers thereof, cyclopentane,
cyclohexane, cycloheptane, cyclooctane and also C.sub.1 -C.sub.4
-alkyl-substituted cycloaliphatics such as methylcyclopentane and
methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and
o-, m- and p-xylene.
The hydrocarbon compound is in general used in a weight ratio of
hydrocarbon compound to oxadimethacrylic I of from 1:1 to 100:1,
preferably from 1:1 to 10:1, particularly preferably from 2:1 to 4:1.
The temperature at the start of the crystallization is advantageously from
5.degree. to 15.degree. C. below the boiling point of the hydrocarbon
compound in order that a very high concentration of oxadimethacrylic I in
the hydro-carbon compound may be obtained. It is also possible to carry
out the crystallization at other temperatures, for example at room
temperature. But in general the range will be from 20.degree. to
200.degree. C., preferably from 40.degree. to 130.degree. C., and it may
be necessary to employ pressures in excess of atmospheric pressure. In
general, the pressure will be within the range from 70 to 250 kPa and is
preferably atmospheric pressure.
If the hydrocarbon compound is not added until the crystallization is to be
initiated, or if the hydrocarbon compound is immiscible or only partially
miscible with the corresponding solvent, it can be advantageous, before
the crystallization, to subject the mixture to intensive mixing by
customary methods such as shaking, stirring or liquid-liquid extraction.
This step can be carried out in one or more stages and continuously or
batchwise. The temperature at which this step is carried out is
advantageously within the abovementioned range from 20.degree. to
200.degree. C., preferably from 40.degree. to 130.degree. C.
The starting materials for the recrystallization will in general be
solutions which contain the oxadimethacrylics in amounts within the range
from 5 to 50, preferably from 10 to 30, % by weight. The solvents used in
these solutions will in general be the abovementioned hydrocarbon
compounds.
The subsequent crystallization of the oxadimethacrylic I is in general
carried out at from (-80) to 30.degree. C., preferably at from (-30) to
20.degree. C. The crystalline product is then separated off in a
conventional manner, for example by filtration or centrifuging, and dried
in a conventional manner.
If, after the crystallization, two or more liquid phases are present, the
phase which is not enriched with the hydrocarbon compound can be separated
off and used in another workup cycle in order that the remaining
quantities of the oxadimethacrylic I may also be obtained. This process
can be repeated ad infinitum and be carried out continuously or batchwise.
The crystallization will in general be repeated until the desired purity
has been obtained.
Oxadimethacrylics I where E and/or E' are each COOH are preferably prepared
by hydrolyzing the oxadimethacrylic ester I where E and E' are each
--COOR.sup.1, or a mixture of various of these esters, in a basic solution
and then acidifying the resulting salt. Then the precipitated acid can be
separated off and, if desired, be recrystallized in an acid aqueous
medium.
The basic solution used will in general be an aqueous solution of an alkali
metal alcoholate such as sodium methoxide, potassium methoxide, sodium
ethoxide, potassium ethoxide, preferably sodium ethoxide, an alkali or
alkaline earth metal hydroxide such as lithium hydroxide, sodium
hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide or
barium hydroxide, preferably sodium hydroxide or potassium hydroxide, or
ammonia.
The reaction medium may include additives such as solubilizers and
polymerization inhibitors. Suitable solubilizers are for example alcohols,
preferably C.sub.1 -C.sub.4 -alcohols such as methanol, ethanol,
n-propanol, isopropanol, n-butanol and tert-butanol, particularly
preferably methanol and ethanol. Preferred polymerization inhibitors are
the customary water-soluble compounds such as hydroquinone, hydroquinone
monoethyl ether and cupric salts.
The free acid is obtained by adding an acid, preferably a mineral acid such
as sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid,
particularly preferably hydrochloric acid, to the reaction medium.
The molar ratio of base to ester will in general be selected within the
range from 1:1 to 5:1, preferably from 2:1 to 4:1. The base will in
general be used in the form of an aqueous solution in concentrations of
from 0.1 to 40, preferably from 1 to 20, % by weight, based on water.
The amount of solubilizer will in general be within the range from 0 to 30,
preferably from 0 to 10, % by weight and the amount of polymerization
inhibitor within the range from 0 to 0.1, preferably from 0 to 0.05, % by
weight, each percentage being based on the total amount of the reaction
mixture.
The amount of acid precipitant used depends on the strength and
concentration of the acid. In general the amount chosen will be such that
the salt-containing medium, in general the reaction mixture, is adjusted
to a pH within the range from 0.5 to 2.0, preferably from 0.5 to 1.5.
The choice of temperature is not critical, judging by experience to date.
In general, the temperature range will extend from 10.degree. to
100.degree. C. under a pressure within the range from 70 to 300 kPa. It is
also possible to carry out the hydrolysis in a pressure reactor at
temperatures above 100.degree. C., but in general not higher than
200.degree. C. However, it is preferable to hydrolyse at from 15.degree.
to 50.degree. C. under atmospheric pressure.
The precipitated oxadimethacrylic acid can be separated off by the usual
methods such as filtration, decanting or centrifuging and, if desired,
purified, for example by washing with cold water and then drying. From
experience to date the oxadimethacrylic acid thus obtained is at least 99%
pure.
Particularly pure oxadimethacrylic acid, for example with a by-product
content of less than 100 ppm, is preferably obtainable by
recrystallization. For this the oxadimethacrylic acid is in general
dissolved in hot water at from 50.degree. to 100.degree. C., preferably at
from 60.degree. to 100.degree. C., particularly preferably at from
80.degree. to 100.degree. C., and then crystallized out at from 5.degree.
to 30.degree. C., preferably at from 10.degree. to 25.degree. C.
Polymerization inhibitors such as hydroquinone monomethyl ether can be
added to the solution in amounts of from 10 to 20 ppm. The solution can
also be treated with adsorbents such as activated carbon, kieselguhr and
zeolites, then filtered hot and thereafter cooled down to bring about
crystallization.
The carboxylic acid groups of the oxadimethacrylic acid obtained can be
further functionalized in a conventional manner to ester, amide and ketone
groups (see Houben-Weyl, Methoden der organischen Chemie, vol. VIII/III,
Thieme, Berlin, 1952, p. 503 ff and p. 647 ff).
Component B) according to the invention comprises from 1 to 99% by weight
of at least one further monomer that is copolymerizable with the
oxadimethacrylics I by a free radical mechanism.
Examples are:
acrylic acid and methacrylic acid,
C.sub.1 -C.sub.20 -alkyl acrylates, preferably the C.sub.1 -C.sub.12 -alkyl
esters, in particular the C.sub.1 -C.sub.4 -alkyl esters such as methyl
acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl
acrylate, and also 2-ethylhexyl acrylate and lauryl acrylate,
C.sub.1 -C.sub.20 -alkyl methacrylates, preferably the C.sub.1 -C.sub.4
-alkyl esters such as methyl methacrylate, ethyl methacrylate, propyl
methacrylate, n-butyl methacrylate and tert-butyl methacrylate, in
particular methyl methacrylate,
C.sub.5 -C.sub.12 -cycloalkyl acrylates such as cyclopentyl acrylate,
cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate,
cyclododecyl acrylate,
C.sub.5 -C.sub.12 -cycloalkyl methacrylates such as cyclopentyl
methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate,
cyclooctyl methacrylate, cyclododecyl methacrylate,
acrylonitrile and methacrylonitrile,
acrylamide and methacrylamide and their N-alkyl and N,N-dialkyl derivatives
with C.sub.1 -C.sub.2 alkyl groups,
vinyl and vinylidene esters of aliphatic C.sub.2 -C.sub.8 -carboxylic acids
such as vinyl acetate,
aromatic vinyl monomers such as styrene and alpha-methylstyrene and their
ring-monosubstituted or -polysubstituted derivatives, for example 2-, 3-,
4-methylstyrene, 2-, 3-, 4-ethylstyrene, 2-, 3-, 4-isopropylstyrene,
4-tert-butylstyrene, 3,4-dimethylstyrene, 2-, 4-chlorostyrene, 2-,
4-bromostyrene, 3,4-dichlorostyrene, vinyltoluene, particularly preferably
styrene, maleic acid, fumaric acid and itaconic acid, C.sub.1 -C.sub.10
-alkyl maleates, fumarates and itaconates, maleamide, fumaramide and
itaconamide and their N-alkyl and N,N-dialkyl derivatives with C.sub.1
-C.sub.10 -alkyl groups, and also mixtures thereof.
Suitable transfer regulators are monofunctional C.sub.1 -C.sub.12 -alkyl
mercaptans such as methyl mercaptan, sec-butyl mercaptan, n-, i- and
tert-dodecyl mercaptan and also thioacetic acid and its C.sub.1 -C.sub.4
-alkyl esters. They are preferably used in amounts of from 0.01 to 5% by
weight, particularly preferably from 0.05 to 2% by weight. To improve the
heat resistance it is preferable to employ amounts ranging from 0.1 to 1%
by weight.
Transfer regulators, which are employed to limit the chain length, have
also been found to improve the thermal stability.
A preferred embodiment concerns monomer mixtures of
A) from 5 to 99, preferably from 10 to 50, % by weight of an
oxadimethacrylate I, preferably dimethyl
2,2'-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl
2,2'-[oxybis(methylene)]bis-2-propenoate or cyclohexyl methyl
2,2'-[oxybis(methylene)]bis-2-propenoate, particularly preferably dimethyl
2,2'-[oxybis(methylene)]bis-2-propenoate or dicyclohexyl
2,2'-[oxybis(methylene)]bis-2-propenoate, and
B) from 0.99 to 94.99, preferably from 49.99 to 89.99, % by weight of a
monomer mixture of
B.sub.1) from 0 to 15, preferably from 1 to 7, % by weight of a C.sub.1
-C.sub.20 -alkyl acrylate, preferably a C.sub.1 -C.sub.4 -alkyl acrylate
such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl
acrylate, tert-butyl acrylate, particularly preferably methyl acrylate.
An acrylate proportion higher than 15% by weight does result in higher
thermal stability and flowability values, but also in general in
excessively reduced heat distortion resistance values.
B.sub.2) From 0 to 94, preferably from 1 to 90, % by weight of a C.sub.1
-C.sub.20 -alkyl methacrylate, preferably a C.sub.1 -C.sub.4 -alkyl
methacrylate such as methyl methacrylate, ethyl methacrylate, propyl
methacrylate, n-butyl methacrylate, tert-butyl methacrylate, particularly
preferably methyl methacrylate.
B.sub.3) From 0 to 20, preferably from 1 to 15, % by weight of at least one
further monomer such as styrene, .alpha.-methylstyrene, vinyl chloride,
acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, or an
acrylic or methacrylic ester.
The polymerization is carried out in the presence of from 0.01 to 5,
preferably from 0.1 to 1, % by weight of n-dodecyl mercaptan.
If alkyl methacrylates are used as monomers B.sub.2 this generally improves
the weathering stability.
The amounts of components B.sub.1) and B.sub.2) will in general be chosen
in such a way that the sum total is within the range from 1 to 93.99% by
weight.
These preferred mixtures can be used for producing transparent molding
materials that are heat distortion resistant. In general they are also
weathering resistant and show high thermal stability in thermoplastic
processing.
The copolymers of the invention are in general prepared in a conventional
manner, for example in bulk or in solution.
In the case of bulk polymerization it is possible to use oil-soluble
initiators (free radical initiators such as diacyl peroxides, peresters
such as tert-butyl perpivalate, peroxidicarbonates, hydroperoxides,
dialkyl peroxides such as dilauroyl peroxide or azo compounds such as
azobisisobutyronitrile).
The polymerization temperature will in general be within the range from
20.degree. to 200.degree. C., preferably from 50.degree. to 160.degree. C.
The molecular weight can be controlled by means of suitable chain transfer
agents such as the commercial mercaptans or by means of suitable
temperature control. In general, molecular weights will be selected to be
within the range from 50,000 to 180,000, preferably from 80,000 to
130,000, g/mol (weight average molecular weight).
The copolymers can also be prepared by solution polymerization. Suitable
solvents are for example toluene, xylene, acetone and tetrahydrofuran. In
other respects the polymerization can be carried out under the conditions
described for bulk polymerization.
Details may be found for example in Houben-Weyl, Methoden der organischen
Chemie, vol. 14/1.
In addition to the essential components A) and B) the copolymers and the
moldings, films and fibers produced therefrom may contain customary
additives and processing aids. The proportion thereof will in general be
up to 5, preferably up to 2, % by weight, based on the total weight of
components A) and B).
Customary additives include for example antioxidants, heat and light (UV)
stabilizers, lubricants, demolders, dyes, pigments, plasticizers,
antistats and flame retardants.
Antioxidants and heat stabilizers suitable for inclusion in the
thermoplastic compounds of the invention are for example sterically
hindered phenols, hydroquinones, phosphites and derivatives and
substituted representatives of this group and mixtures thereof, preferably
in concentrations up to 1% by weight, based on the weight of the mixture.
Examples of UV stabilizers are substituted resorcinols, salicylates,
benzotriazoles and benzophenones, which in general can be used in amounts
of up to 1% by weight.
Lubricants and demolders, which in general can be added to the
thermoplastic compound in amounts of up to 1% by weight, are for example
stearic acid, stearyl alcohol, alkyl stearates, N-alkylstearamides and
also esters of pentaerythritol with long-chain fatty acids. Suitable dyes
are organic dyes, for example anthraquinone red, organic pigments and
lakes such as phthalocyanine blue, inorganic pigments such as titanium
dioxide and cadmium sulfide. Suitable plasticizers are for example dioctyl
phthalate, dibenzyl phthalate and butyl benzyl phthalate.
The flame retardant used can be for example a phosphorus-containing
compound in amounts of from 1 to 40% by weight.
Flame retardants of this type are for example organic phosphorus compounds
such as the esters of phosphoric acid, phosphorous acid, phosphonic acid
and phosphinic acid and also tertiary phosphines and phosphine oxides. An
example is triphenylphosphine oxide.
Suitable flame retardants also include compounds with phosphorus-nitrogen
bonds, such as phosphonitrilic chloride, phosphoric ester amides,
phosphoramides, phosphinamides, tris(aziridinyl)phosphine oxide or
tetrakis(hydroxymethl)phosphonium chloride.
The additives can be added at any stage of the process, but stabilizers are
advantageously added early in order to have protection right from the
start. Accordingly, the stabilizers will in general be added even during
the polymerization, provided that they do not interfere with it.
The copolymers of the invention can be processed by customary methods, for
example by injection molding, extrusion molding or sintering to produce
moldings, films or fibers.
The copolymers, moldings, films and fibers produced by the process of the
invention have the advantage over known oxadimethacrylic copolymers of
being soluble and thermoplastically processible.
The copolymers of the invention can be processed into thermoplastically
processible molding materials that are heat distortion resistant.
A further preferred embodiment concerns monomer mixtures of
A) from 1 to 99% by weight, preferably from 1 to 40% by weight, of monomer
I,
B) from 99 to 1% by weight, preferably from 99 to 60% by weight, of C.sub.1
-C.sub.20 -alkyl methacrylate,
C) from 0 to 20% by weight, preferably from 1 to 10% by weight, of C.sub.1
-C.sub.20 -alkyl acrylate, and
D) from 0 to 20% by weight, preferably from 1 to 10% by weight, of other
monomers.
Preferred monomers I are those in which the groups E and E' are each
--COOR.sup.1 where R.sup.1 has the aforementioned meaning, in particular
where R.sup.1 is particularly preferably methyl or cyclohexyl.
Particularly preferred monomers I contain less than 1,000 ppm, preferably
less than 500 ppm, particularly preferably less than 100 ppm, of
impurities, for example in the form of oligomers.
Suitable C.sub.1 -C.sub.20 -alkyl methacrylates are the aforementioned
compounds recited by way of example, in particular methyl methacrylate.
Suitable C.sub.1 -C.sub.20 -alkyl acrylates are the aforementioned
compounds recited by way of example, in particular methyl, ethyl,
n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, tert-butyl, pentyl,
hexyl, heptyl, 2-ethylhexyl or octyl acrylate, particularly preferably
methyl, ethyl or n-butyl acrylate.
In general, additions of alkyl acrylates bring about an improvement in the
flame polishability and in sawability and also an increase in the thermal
stability.
Other monomers are preferably in particular those compounds which, after
the polymerization, do not reduce the glass transition temperature to any
significant extent, if at all. Examples are the aforementioned aromatic
vinyl monomers, in particular styrene and alphamethylstyrene, and also
maleic anhydride and maleamide and its N-alkyl and N,N-dialkyl
derivatives.
To increase the stress cracking resistance, the monomer mixture may include
from 0 to 5, preferably from 0 to 1, % by weight of multifunctional
compounds with methacryloyl or acryloyl groups as crosslinkers. Examples
are: allyl methacrylate, allyl acrylate, 1,4-butanediol dimethacrylate,
1,4-butanediol acrylate, ethylene glycol dimethacrylates ethylene glycol
diacrylate, 1,3-butanediol dimethacrylate, 1,3-butanediol diacrylate,
1,6-hexanediol dimethacrylate, 1,6-hexanediol diacrylate, polyethylene
glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene
glycol dimethacrylate, tetraethylene glycol diacrylate, trimethylolpropane
trimethacrylate, trimethylolpropane triacrylate,
2,2-dimethyl-1,3-propanediol dimethacrylate and divinylbenzene.
Furthermore, in particular if cast glass plates are to be manufactured,
from 0 to 5, preferably from 0.1 to 4, particularly preferably from 0.5 to
3, % by weight can be added of a demolding aid. Examples of the molding
aids are: stearic acid, cellulose derivatives, lecithin, diglycerides of
stearic, palmitic and oleic acid, long-chain fatty alcohols such as cetyl
alcohols, stearyl alcohol and also long-chain phosphoric esters.
The polymerization is in general carried out as described above or by the
general chamber polymerization methods described in the literature (see
Kunststoff-Handbuch, volume IX, Polymethacrylate, Carl-Hanser-Verlag,
1975, pages 15-21).
Depending on the use, the monomer mixture may be stabilized with from 0.01
to 1% by weight of customary UV stabilizers such as benzotriazoles,
benzophenones, cyanoacrylates or oxamides and in particular hindered amine
light stabilizers (HALS) such as the succinic or glutaric esters of
2,2,6,6-tetramethylpiperidin-4-ol mentioned in EP-A-243,319.
It may furthermore contain, in an amount of p to 40% by weight, customary
additives such as flame retardants, antistats or fillers.
The polymers prepared in this way are useful in particular for
manufacturing cast glass plates of enhanced heat distortion resistance,
the target molecular weight average (M.sub.w) being in general greater
than 10.sup.6 g/mol and the residual monomer content less than 2% by
weight. Cast glass plates thus manufactured have from observations to date
a lower breakage rate than conventional cast glass plates, since they are
easier to demold.
EXAMPLES
A) Examples without transfer regulator
Example 1
6 g of dimethyl 2,2'-[oxybis(methylene)]bis-2-propenoate (99.5% pure), 14 g
of methyl methacrylate, 0.02 g of dilauroyl peroxide, 0.04 g of tert-butyl
perpivalate and 80 g of tetrahydrofuran were heated at 65.degree. C. for
24 h. After cooling, 1000 ml of methanol were added, and the resulting
copolymer precipitate was filtered off and dried at 50.degree. C. under a
pressure of 10 kPa leaving 18.6 g (93%) of a completely tetrahydrofuran
and chloroform soluble copolymer having a viscosity number of 80 (measured
on a 0.5% by weight solution in chloroform).
Example 2
Example 1 was repeated with a 99.2% pure oxadimethacrylate, affording 18.4
g (92%) of a completely tetrahydrofuran and chloroform soluble copolymer
having a viscosity number of 83 (measured on a 0.5% by weight solution in
chloroform). The glass transition temperature T.sub.g was 127.degree. C.
Example 3
Example 2 was repeated with 14.0 g of styrene instead of the methyl
acrylate. This produced 14.4 g (72%) of a completely tetrahydrofuran and
chloroform soluble copolymer having a viscosity number of 53 (measured on
a 0.5% by weight solution in chloroform) and a glass transition
temperature T.sub.g of 149.degree. C.
Example 4
Example 3 was repeated using instead of the dimethyl
2,2'-[oxybis(methylene)]bis-2-propenoate, 6.0 g of the dicyclohexyl ester
(purity 99.5%). This produced 15.3 g (77%) of a completely tetrahydrofuran
and chloroform soluble copolymer having a viscosity number of 57 (measured
on a 0.5% by weight solution in chloroform) and a glass transition
temperature T.sub.g of 124.degree. C.
Comparative Example 1
Example 1 was repeated with a 95.0% pure oxadimethacrylate, affording 19.0
g (95%) of a tetrahydrofuran and chloroform insoluble copolymer.
B) Examples with transfer regulator
Example 5
6 g of dimethyl 2,2'-[oxybis(methylene)]bis-2-propenoate (purity 99.2%),
0.3 g of methyl acrylate, 13.7 g of methyl methacrylate, 0.02 g of
dilauroyl peroxide, 0.04 g of tert-butyl perpivalate, 0.04 g of n-dodecyl
mercaptan and 80 g of tetrahydrofuran were heated at 65.degree. C. for 24
h. After cooling, 1000 ml of methanol were added, and the resulting
copolymer precipitate was filtered off and dried at 50.degree. C. under a
pressure of 10 kPa, leaving 16.3 g (81%) of a completely tetrahydrofuran
and chloroform soluble copolymer having a viscosity number of 57 (measured
on a 0.5% by weight solution in chloroform).
Examples 6 to 11
Except in the case of Example 7 (20.6 g of monomer mixture) in each case 20
g of a monomer mixture (see table) were polymerized and worked up as
described in Example 5.
The glass transition temperature T.sub.g was determined by the DSC method
(ASTM D 3418-82).
Thermal stability was determined as follows. Samples of the substances
produced in the examples were heated by means of a thermogravimetric
analyzer (TGA-M3 from Mettler) to 490.degree. C. at a heating-up rate of
20.degree. C./min while the change in weight was recorded. A plot of the
relative weight (weight of sample at a certain temperature/initial weight
at room temperature) versus the temperature produced in each case a curve
with three parts: (a) an upper, almost horizontal branch until parts of
the sample began to decompose, (b) an adjoining descending branch for the
period in which the bulk of the sample decomposed, and (c) a lower,
horizontal branch which indicates that the decomposition of the polymer
sample is complete.
Two straight lines were then defined as asymptotes to the branches (a) and
(b). One of the straight lines is obtained by extending the uncurved
portion of curve (a) and the other by forming the tangent at the point of
inversion of curve portion (b). Thermal stability, then, is the
characteristic temperature T.sub.z at the point of intersection of the two
straight lines. The arithmetic work was done using a Mettler computer
program installed on the thermogravimetric analyzer.
The results of the individual quality control tests can be seen in Table 1.
They show that the copolymers of the invention are superior in thermal
properties not only to the pure polymethyl methacrylates but also to the
known, insoluble oxadimethacrylate copolymer.
TABLE 1
__________________________________________________________________________
Examples with transfer regulator
Oxadimethacrylate Solubility
CH.sub.2 .dbd.C(COOR)CH.sub.2 --O--CH.sub.2 C(COOR').dbd.CH.sub.2
Methyl
Methyl n-Dodecyl
in THF &
T.sub.g
T.sub.z
Ex.
R R' acrylate
methacrylate
mercaptan
CHCl.sub.3
[.degree.C.]
[.degree.C.]
__________________________________________________________________________
5 Me Me.sup.1)
6 g 0.3 g
13.7 g 0.04 g
completely
138
382
6 cyclohexyl
cyclohexyl.sup.2)
6 g 0.3 g
13.7 g 0.04 g
completely
123
382
7 Me Me.sup.1)
20 g 0.6 g
0 0.08 g
completely
162
335
8 cyclohexyl
Me.sup.2)
6 g 0.4 g
13.6 g 0.06 g
completely
131
334
9 Me Me.sup.1)
6 g 0 14.0 g 0.04 g
completely
141
361
for comparison
10 -- -- 0 g 0.3 g
19.7 g 0.04 g
completely
114
327
11 Me Me.sup.3)
6 g 0 14.0 g 0 insoluble
-- --
__________________________________________________________________________
.sup.1) Purity 99.2%
.sup.2) Purity 99.5%
.sup.3) Purity 95.0%
Examples 12 to 17
The starting materials specified below in Table 2 were initially mixed in a
500 ml flask and then devolatilized under reduced pressure. Then 0.002% by
weight of azobisisobutyronitrile (AIBN) was added, and the mixture was
heated under N.sub.2 to 75.degree. C. and left at that temperature for 70
min. Then 0.02% by weight of tert-butyl perpivalate and 0.06% by weight of
tert-butyl perisononanoate were added to the mixture. The mixture thus
prepared was introduced into a silicate glass plate chamber measuring 250
mm.times.250 mm.times.4 mm. The chamber was then sealed and its contents
were polymerized in a water bath at the following temperatures:
1 h at 65.degree. C., then
4 h at 55.degree. C., and
2 h at 75.degree. C.
The reaction mixture was then postpolymerized in a drying cabinet at
120.degree. C. for 3 h.
TABLE 2
______________________________________
Isostearic
Breakage
MMA (I).sup.1)
(II).sup.2)
BDA2.sup.3)
acid rate.sup.4)
No. (%) (%) (ppm) (%) (%) (%)
______________________________________
12 90 10 100 -- -- 80
13 90 10 100 -- 0.5 0
14 69 30 100 1.0 0.5 0
for comparison
15 90 10 1500 -- -- 100
16 90 10 1500 -- 0.5 60
17 69 30 1500 1.0 0.5 60
______________________________________
.sup.1) Oxadimethacrylate (E.dbd.E'.dbd.COOMe)
.sup.2) Proportion of oligomer in (I)
.sup.3) Butanediol diacrylate
.sup.4) Proportion of acrylate glass plates breaking on demolding in 5
attempts in each case
Examples 12 and 15 show that a smaller oligomer content ameliorates the
breakage rate.
Examples 13 and 16 document the positive difference of isostearic acid in
connection with an oligomer content of 100 ppm.
Examples 14 and 17 show that the addition of the crosslinking agent BDA2
has neither an ameliorating nor worsening effect on the breakage rate.
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